Redox regulation of Ni hydroxides with controllable phase composition towards biomass-derived polyol electro-refinery.

Electrocatalytic refinery from biomass-derived glycerol (GLY) to formic acid (FA), one of the most promising candidates for green H2 carriers, has driven widespread attention for its sustainability. Herein, we fabricated a series of monolithic Ni hydroxide-based electrocatalysts by a facile and in situ electrochemical method through the manipulation of local pH near the electrode. The as-synthesized Ni(OH)2@NF-1.0 affords a low working potential of 1.36 VRHE to achieve 100% GLY conversion, 98.5% FA yield, 96.1% faradaic efficiency and ∼0.13 A cm-2 of current density. Its high efficiency on a wide range of polyol substrates further underscores the promise of sustainable electro-refinery. Through a combinatory analysis via H2 temperature-programmed reduction, cyclic voltammetry and in situ Raman spectroscopy, the precise regulation of synthetic potential was discovered to be highly essential to controlling the content, phase composition and redox properties of Ni hydroxides, which significantly determine the catalytic performance. Additionally, the 'adsorption-activation' mode of ortho-di-hydroxyl groups during the C-C bond cleavage of polyols was proposed based on a series of probe reactions. This work illuminates an advanced path for designing non-noble-metal-based catalysts to facilitate electrochemical biomass valorization.

Directional Electrosynthesis of Adipic Acid and Cyclohexanone by Controlling the Active Sites on NiOOH.

Dicarboxylic acids and cyclic ketones, such as adipic acid (AA) and cyclohexanone (CHN), are essential compounds for the chemical industry. Although their production by electrosynthesis using electricity is considered one of the most promising strategies, the application of such processes has been hampered by a lack of efficient catalysts as well as a lack of understanding of the mechanism. Herein, a series of monolithic msig/ea-NiOOH-Ni(OH)2/NF were prepared by means of self-dissolution of metal matrix components, interface growth, and electrochemical activation (denoted as msig/ea). The as-synthesized catalysts have three-dimensional cuboid-like structures formed by interconnecting nanosheets composed of NiOOH. By theoretically guided regulation of the amounts of Ni3+ and oxygen vacancies (OV), a 96.5% yield of CHN from cyclohexanol (CHA) dehydrogenation and a 93.6% yield of AA from CHN oxidation were achieved. A combined experimental and theoretical study demonstrates that CHA dehydrogenation and CHN oxidation were promoted by the formation of Ni3+ and the peroxide species (*OOH) on OV. This work provides a promising approach for directional electrosynthesis of high-purity chemicals with in-depth mechanistic insights.

Activating Commercial Nickel Foam to a Highly Efficient Electrocatalyst for Oxygen Evolution Reaction through a Three-Step Surface Reconstruction.

It is highly desired to directly use commercial nickel foam (CNF) as an electrocatalyst for the oxygen evolution reaction (OER) via simple surface reconstruction. In our research, a simple three-step preactivation process was proposed to reconstruct CNF as an efficient OER catalyst, including calcination, high-voltage treatment, and immersing in electrolyte. The optimal CNF after three-step activation reaches an excellent OER performance of 228 and 267 mV at η10 and η100 in alkaline media and can tolerate long-term tests under a large current density of 500 mA·cm-2. The promotion of each step was explored. The calcination step leads to a reconstructive surficial morphology with an enlarged active surface, providing a prerequisite for the following construction steps. The high-voltage treatment changes the valence of surface Ni species, generating phases with higher catalytic activity, and the immersing process introduces Fe heteroatoms into the surface of CNF, boosting the catalytic performance of CNF through Ni-Fe interactions. This research provides a simple method of making high-performance catalysts with accessible nickel foam, a potential for large-scale application in practical industry, and new thinking for the manipulation of Ni-based catalysts.

Electronic Structure Engineering of Pt Species over Pt/WO3 toward Highly Efficient Electrocatalytic Hydrogen Evolution.

Pt-based supported materials, a widely used electrocatalyst for hydrogen evolution reaction (HER), often experience unavoidable electron loss, resulting in a mismatching of electronic structure and HER behavior. Here, a Pt/WO3 catalyst consisting of Pt species strongly coupled with defective WO3 polycrystalline nanorods is rationally designed. The electronic structure engineering of Pt sites on WO3 can be systematically regulated, and so that the optimal electron-rich Pt sites on Pt/WO3 -600 present an excellent HER activity with only 8 mV overpotential at 10 mA cm-2 . Particularly, the mass activity reaches 7015 mA mg-1 at the overpotential of 50 mV, up to 26-fold higher than that of the commercial Pt/C. The combination of experimental and theoretical results demonstrates that the O vacancies of WO3 effectively mitigate the tendency of electron transfer from Pt sites to WO3 , so that the d-band center could reach an appropriate level relative to Fermi level, endowing it with a suitable Δ G H ∗ $\Delta {G_{{{\rm{H}}^ * }}}$ . This work identifies the influence of the electronic structure on catalytic activity.

Colloidal magnesium hydroxide Nanoflake: One-Step Surfactant-Assisted preparation and Paper-Based relics protection with Long-Term Anti-Acidification and Flame-Retardancy.

Enhancing the interfacial dispersion and suspension stability is crucial for magnesium hydroxide (Mg(OH)2) nanomaterials in the long-term deacidification of paper-based cultural relics. However, because of the low specific surface area and the poor solvent compatibility of as-prepared large-sized Mg(OH)2, it often tends to agglomerate and settle down during the usage and storage, that is harmful for paper protection due to its unevenly deacidification and nonuniformly distribution on paper cellulose. Herein, we propose a feasible preparation of colloidal Mg(OH)2 ultrathin nanoflakes with high dispersion stability via a simple one-step surfactant-assisted strategy. The surfactant acts as both a structure-direct agent to confine the growth of Mg(OH)2 with rich active sites and a surface modifier to enhance its solvent adaptability and dispersion stability, avoiding the common fussy procedure with additional steric stabilizer. Owing to the evenly interaction with free acid species therein and the uniformly distribution on the paper fiber as alkaline reserve, the as-obtained Mg(OH)2 presents the superior paper protection performance characterized by its safer pH of 7.29 for the original aged paper (pH = 5.03) and the excellent long-term anti-acidification effect with competitive pH of 5.47 after accelerated-aging at 105 °C for 5 months. Furthermore, Mg(OH)2 nanoflakes with surfactant-modified structure also endue them as an improved flame retardant for multifunctional paper protection. The protection with Mg(OH)2 has little effect on the paper surface properties and cellulose crystallinity, in line with the principle of least intervention. This work will put forward a feasible way toward colloidal Mg(OH)2 nanoflakes with excellent paper protection performance, shedding light on the development of emerging protection materials for paper-based cultural relics.

Two-dimensional quasi-nanosheets enabled by coordination-driving deposition and sequential etching.

Transition-metal compounds are attractive for catalysis and other fields but generally suffer from aggregating propensity, circuitous diffusion pathways and limited reaction activities. Two-dimensional (2D) quasi-nanosheets composed of nano-sized crystals with precisely controlled stoichiometric features can readily overcome these problems. We here construct a variety of interconnected 2D holey arrays composed of single-crystal nitrogen-doped nanoparticles through a coordination-driving deposition and sequential etching (CDSE) strategy, independent of the phases and stoichiometries of target crystals. The strong coordination between the empty orbits of metal ions and n-orbits of pyridine nitrogen in conjugated carbon nitride (CN) confines the growth of metal species in 2D form. Meanwhile, the eighteen-membered-rings of CN coupled with metal ions can be thermally etched preferentially as a result of weakened N[double bond, length as m-dash]C bonds caused by forming the TiO2+-N6 configuration. The as-obtained metal oxide quasi-nanosheets and their phosphatized counterparts show impressive activities in photocatalysis and electrocatalysis owing to the synergetic effect of geometric and compositional features. Our CDSE strategy offers a versatile platform, with which to explore the properties and functions of hierarchical architectures.

Ultrathin dodecyl-sulfate-intercalated Mg-Al layered double hydroxide nanosheets with high adsorption capability for dye pollution.

A high-performance dye adsorbent of ultrathin dodecyl-sulfate (DS-) intercalated Mg-Al layered double hydroxide nanosheets (DI-LDH Ns) were controllably synthesized by a simple one-step surfactant-assisted hydrothermal method. The unique intercalated structure with week interlayer interaction and high accessible surface of DI-LDH Ns provide efficient adsorption of methyl orange (MO), leading to its superior performance with much higher uptake capability (846.6 mg/g at 298 K) and less adsorbing equilibrium time (5 min) than those of ultrathin DS--surface-modified Mg-Al-LDH nanosheets (DM-LDH Ns, 327.4 mg/g at 298 K, 120 min) and original Mg-Al-LDH (O-LDH, 208.2 mg/g at 298 K, 120 min). The composition and structure of these LDHs were investigated by systematic physicochemical characterization, such as XRD, TEM, FT-IR, BET and TGA. The adsorption behavior of DI-LDH Ns follows the Langmuir isotherm equation. A plausible mechanism is proposed to explain the adsorption process of such DI-LDH Ns, in which the synergistic contributions of surface and interlayer adsorption between DI-LDH Ns and MO play an important role. This study puts forward a new thought for the development of high-performance LDH adsorbents with an ultrathin intercalated structure for the efficient and rapid removal of dyes.